1. Technical Field of the Invention
This invention relates to a method for the preparation of predominantly linear polyethylenepolyamines by reacting ethylenediamine with monoethanolamine in the presence of an intercalatively catalytically active tetravalent zirconium polymeric reaction product of an organo-phosphonic acid or an ester thereof with a compound of tetravalent zirconium reactive therewith.
The catalysts that are used in accordance with the present invention are solid polymeric reaction products of an organo-phosphonic acid or an ester thereof with a tetravalent zirconium compound. The polymeric reaction products display intercalation activity, have a layered structure, and may be further characterized as having a molar ratio of phosphorous to zirconium of about 2 to 1 and as having a molecular structure such that the organo groups of the polymeric reaction product are covalently bonded to phosphorous through a carbon linkage and such that the phosphorous is linked to the zirconium through an oxygen linkage.
2. Prior Art
Heretofore, polyethylenepolyamine compounds such as diethylenetriamine, triethylenetetramine and the higher homologs have been produced by the reaction of an alkyl halide such as ethylene dichloride with an amine such as ammonia or ethylenediamine at elevated temperatures and pressures. Normally, relatively high yields of predominantly noncyclic polyethylenepolyamine compounds are obtained from this process with varying yields of heterocyclic amines. The large amounts of energy required to produce the reactants as well as the difficult separation procedures required to recover the more valuable linear polyethylenepolyamines diminish the utility of the ethylene dichloride process. The hydrohalide salts of ammonia and the polyethylenepolyamine products must also undergo difficult and time consuming caustic neutralization to yield the free polyethylenepolyamines.
Investigators have found that more linear products can also be obtained in a catalytic conversion. Thus, Ford et al. U.S. Pat. No. 4,316,840 discloses the preparation of polyalkylenepolyamines from ethylenediamine utilizing a metal nitrate or sulfate as a catalyst. U.S. Pat. No. 4,314,083 discloses the reaction of ethylenediamine with monoethanolamine to prepare noncyclic polyalkylenepolyamines using, as a catalyst, a salt of a nitrogen or sulfur-containing compound.
Ford et al. U.S. Pat. No. 4,362,886 discloses a process for preparing predominantly non-cyclic polyalkylenepolyamine compounds from feedstocks such as ethylenediamine and ethanolamine using a compound of antimony, bismuth or arsenic as a catalyst. In Ford et al. U.S. Pat. No. 4,399,308, a Lewis acid halide is used to catalyze the reaction. In European patent application No. 0073520, Ford et al. disclose the use of a phosphorous-containing substance such as boron phosphate or a salt of a sulfur-containing substance such as beryllium sulfate, boron sulfate or ammonium sulfate as the catalyst.
Brennan et al. U.S. Pat. No. 4,036,881 discloses the use of phosphorous-containing catalysts to catalyze the reaction of ethylenediamine with monoethanolamine.
In copending application Ser. No. 455,154 in the name of Vanderpool filed Jan. 3, 1983, and entitled "Catalytic Preparation of Linear Polyethylenepolyamines with Supported Catalyst", a process for the preparation of linear polyethylenepolyamines is disclosed wherein monoethanolamine is reacted with ethylenediamine in the presence of zirconium silicate to which phosphorous has been thermally bonded. Copending Vanderpool patent application Ser. No. 455,160 filed Jan. 3, 1983, and entitled "Catalysts and Preparation of Linear Polyethylenepolyamines Therewith" discloses the use of zirconia having phosphorous thermally bonded thereto as a catalyst for promoting the reaction of ethylenediamine with monoethanolamine to provide essentially linear polyethylenepolyamine reaction products.
French Pat. No. 1,317,359 dated Feb. 8, 1963, discloses the preparation of granulated zirconium phosphate and its use as an ion-exchange resin. Winkler et al. in a 1966 publication [Deutsche Akad. Wiss., Berlin, Germany, Z. Anorg. Allgen. Chem. 346 (1-2), 92-112 (1966)] disclose compounds of the general formula HX.sup.v P.sub.2 O.sub.3 wherein X represents arsenic, antimony and mixtures thereof. Also disclosed are compounds of the general formula H.sub.2 X.sup.iv P.sub.2 O.sub.3, wherein X represents silicon, germanium, tin, lead, titanium and zirconium. It is shown that the group IV phosphates have cation exchange properties.
DiGiacomo et al. U.S. Pat. No. 4,256,872 issued Mar. 17, 1981, contains a comprehensive disclosure of layered organo phosphorous inorganic polymers and methods of preparing such polymers. The patentees broadly disclose a process for the production of inorganic polymers having organo groups covalently bonded to phosphorous atoms and in which the phosphorous atoms are, in turn, covalently bonded by an oxygen linkage to a tetravalent metal atom to provide layered crystalline reaction products wherein the organo groups are present on the apparent and interlamellar surfaces. It is pointed out by the patentees that many inorganic solids crystallize to form a layered structure in which sheets or slabs of a thickness of from 1 to 7 atomic diameters lie upon one another. Such polymers can have strong ionic or covalent bonds within the intra sheet structure while having relatively weak van der Waals or hydrogen bonding between the interlamellar basil surfaces in the direction perpendicular to their planes. As a consequence, "guest" species of other chemical compounds can be incorporated between the lamella. The process, designated by the patentees as "intercalation" is one wherein the incoming guest molecules cleave the layers apart and occupy the region between them leaving the layers virtually intact since the crystals swell in only one dimension, i.e., perpendicular to the layers. A related disclosure is found in DiGiacomo et al. U.S. Pat. No. 4,298,723 issued Nov. 3, 1981.